Process for breaking petroleum emulsions employing certain oxyalkylated amine-modified thermoplastic phenolaldehyde resins



PROCESS FOR BREAKING PETROLEUM EMUL- SIONS EMPLOYING CERTAIN OXYALKYLATED AMlNE-MODIFIED THERMOPLASTIC PHENOL- ALDEHYDE RESINS Melvin De Groote, University City, Mo., assignonto Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application March 25, 1954 Serial No. 418,786

Claims. 01. 252-344 The present invention is a continuation-in-part of my co-pending application, Serial No. 398,632, filed December 16, 1953, now abandoned.

This invention relates to processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions.

My invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the invention.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil. Y

Attention is directed to my co-pending application, Serial No. 398,632, filed December 16, 1953, which relates to a process for breaking petroleum emulsions employing a demulsifier including products obtained by condensing certain phenol aldehyde resins, therein described in detail, with certain basic secondary amines, also therein described in detail, and alpha-hydroxyadipaldehyde.

The present invention may be characterized in that it is concerned with a process for breaking petroleum emulsions employing demulsifiers including the above described reaction products of Serial No. 398,632 further oxyalkylated by means of certain monoepoxides, hereinafter described in detail.

The products obtained by oxyalkylation with a monoepoxide such as ethylene oxide, propylene oxide, butylene oxide, or the like, can be subjected to further reaction with a product having both a nitrogen group and 1,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of Patented Jan. 7,1958

various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents, as, for example, for cosmetics spray oils, water-repellent textile finishes; as lubricants,

etc.

In the presentinstance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they arein many instances. If such compounds are not Xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as cthyleneglycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

Reference is made to U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. Attention is directed to that part of the text which appears in columns 28 and 29, linesl2 through 75, and lines l'through 21, respectively. Reference is'made to this-test with the same force and effect as if it were herein included. This, in essence, means that the preferred product for resolution of petroleum emulsions of the water-in-oil type is characterized by the fact that a 50-50 solution in xylene, or its equivalent, when-mixed with one to three voltunes of water and shaken will produce an emulsion.

For purpose of convenience, what is said hereinafter will be divided into five parts Part 1 isiconcerned with, phenol-aldehyde resins suitable for condensation; I

Part2 is concerned with suitable secondary amines which can be employedin conjunction with the resins in the condensation procedure,

Part3 is concerned with the condensation procedure as such;

Part 4 is concerned with reactions involving the intermediates obtained in the manner described in Part 3, preceding, and certain alpha-beta monoepoxides having not over 4 carbon atoms;

Part 5 is concerned with the resolution of petroleum emulsions of the water-in-oil typefby means of the previously described chemical compounds or reaction products.

'PART 1 This part is concerned with the preparation of phenolaldehyde resins of the kind described in detail in U. S. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, with the following qualifications; said afore mentioned patent'is limited to resins obtained from difunctional phenols having 4 to 12 carbon atoms in the substituent hydrocarbon radical. For the present purpose the substituent may have as many as 18 carbon atoms, as in the case of resins prepared from tetradecylphenol,

3 substantially para-tetradecylphenol, commercially available. Similarly, resins can be'prepared from hexadecylphenol or octadecylphenol. This feature will be referred to subsequently.

In addition to U. S. Patent No. 2,499,370, reference is made also to the following U. S. patents: Nos. 2,499,365, 2,499,366, and 2,499,367, all dated March 7, 1950, to De Groote and Keiser. These patents, along with the other two previously mentioned patents, describe phenolic resins of the kind herein employed as initial materials.

For practical purposes, the resins having 4 to 12 carbon atoms are most satisfactory, with the additional C carbon atoms also being very satisfactory. The increased cost of the C and C carbon atom phenol renders these raw materials of less importance, at least at the present time.

Patent 2,499,370 describes in detail methods of preparing resins useful as intermediates for preparing the prodnets of the present application, and reference is made to that patent for such detailed description and to Examples 1a through 103a of that patent for examples of suitable resins.

As previously noted, the hydrocarbon substituent in the phenol may have as many as 18 carbon atoms, as illustrated by tetradecylphenol, hexadecylphenol'and octadecylphenol, reference in each instance being to the difunctional phenol, such as the orthoor para-substituted phenol or a mixture of the same. Such resins are described also in issued patents, for instance, U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser, such as Example 71a.

Reference has been made to an earlier formula which was in essence an over-simplification representing a phenol-formaldehyde resin. Actually, some other aldehyde, such as acetaldehyde, propionaldehyde, or butyraldehyde, may be used. The resin unit can be exemplified thus:

OH I OH "1 OH ln onmfi R R n R in which R is the divalent radical. obtained from the particular aldehyde employed to form the resin.

As previously stated, the preparation of resins of the kind herein employed as reactants is well known. See U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. Resins can be made using an acid catalyst or basic catalyst or a catalyst showing neither acid nor basic properties in the ordinary sense, or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reactiondescribed proceeded more rapidly in the presence of a small amount of free base. The amount may be as small as a 200th of a percent and as much as a few tenths of a percent. Some-. times moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins We found no reason for using other than those which are lowest in price and most readily available commercially. For pura pose of convenience suitable resins are characterized in the following table:

TABLE I M01. wt. Ex. Position m of res n ample R of R derived n molecule b r from- (based on n+2) Phenyl Para Formal- 3. 5 992. 5

dehyde. Tertiary butyl do .d0 3. 5 882. 5 Secondary butyl. Ortho-.. do. 3. 5 882. 5 Oyclohexyl Para do 3. 5 1,025. 5 Tertiary amyl do do 3. 5 959. 5 Mixed secondary Ortho do. 3. 5 805. 5

and tertiary amyl. Propyl 3. 5 805. 5 Tertiary hexyl 3. 5 1, 036. 5 Octyl 3. 5 1. 190. 5 3. 5 L 267. 5 eeyl 3. 5 1, 344. 5 0decyl. 3. 5 1, 498 5 Tertiary butyl 3. 5 9 5 Tertiary amyl 3. 5 1, 022. '5 Nonyl I 3. 5 1,330.5 Tertiary butyl 3. 5 1,071. 5

Tertiary amyl 3. 5 1, 148. 5 Nonyl 3. 5 1,456. 5 Tertiary butyl 3. 5 1,008. 5

Tertiary amyl 3. 5 1, 085. 5 Nonyl 3. 5 1, 393. 5 Tertiary butyl. 4. 2 996.6

Tertiary amyl... 4. 2 1,083. 4 onyl 4. 2 l, 430. 6 Tertiary butyl, 4. 8 1, 094.4 Tertiary army]... 4. 8 1, 189. 6 4. 8 1, 570. 4 1. 5 604. 0 l. 5 646. 0 1. 5 653. 0 1. 5 688. 0

$238 Hexyl 0 Cyelohexyl 0 0 PART 2 As noted previously, a variety of secondary amines free from a primary amino group may be employed. These amines fall into five categories, as indicated previously.

One category consists of strongly basic secondary monoamines free from hydroxyl groups whose composition may be indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radical and may be heterocyclic in a few instances as in the case of piperidine and a secondary amine derived from furfurylamine by methylation or ethylation, or a similar procedure.

Another example of a heterocyclic amine is, of course, morpholine.

The secondary amines most readily available are, of course, amines such as dimethylamine, methylethoamine, diethylamine, dipropylamine, ethylpropylamine, dibntylamine, diarnylamine, dihexylamine, dioctylamine, and dinonylamine. Other amines include bis(l,3-dirnethylbuty1)amine. There are, of course, a variety of primary amines which can be reacted with an alkylating agent such as dimethyl sulfate, diethyl sulfate, an alkyl bromide, an ester of sulfonic acid, etc., to produce suitable amines within the herein specified limitations. For example, one can methylate alphamethylbenzylamine, or benzylamine itself, to produce a suitable reactant. one can us secondary amines such as dicyclohexylamine,

Needless to say,

dibutylamine .or amines containing .one cyclohexyl group and one alkylgroup, or one benzyl group and one alkyl group, such as ethylcyclohexylamine, ethylbenzylamme, etc.

Other suitable compounds are exemplified by Other somewhat similar secondary amines are those of the composition as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other amines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylarm'ne or the alkylation of similar primary amines, or, for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma-phenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and betaphenoxypropylamine.

Other suitable amines are the kind described in British Patent No. 456,517 and may be illustrated by C H -OCH CH -O-CH CH NHCH The secondary category represents secondary amines which are hydroxylated monoamines. These may be illustrated by diethanolamine, methylethanolamine, dipropanolamine, dibutanolamine and ethylpropanolamine. Suitable primary amines which can be so converted into secondary amines include butylamine, amylamine, hexylamine, higher molecular Weight amines derived fromfatty acids, cyclohexylamine, benzylamine, furfurylamine, etc.

Other suitable amines include Z-amino-l-butanol, '2- amino 2 methyl-l-propanol, 2-arnino-2-methyl-l,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, and tris-(hydroxyethyl)aminoethane. Another example of such amines is illustrated by 4-amino-4-methyl-2-pentanol.

Other suitable compounds are the following:

or comparable compounds having two hydroxylate'd groups of different lengths as in (H0 CH3 OHaO 01120 20 GH2CHI) NH HO GgIL Other examples of suitable amines include alphamethylbenzylamine and monoethanolamine; also amines obtained by treating cyclohexylmethylamine with one mole of an oxyalkylating agent as previously described; betaethylhexylbutanolamine, diglycerylamine, etc. Another type of amine which is of particular interest because it includes a very definite hydrophile group includes sugar amines such as glucamine, galactamine and fructarnine, such as N- hydroxyethylglucamine, N-hydroxyethylgalactamine, and N-hydroxyethylfmctamine.

Other suitable amines may be illustrated by CH3 H-O. CH2...C'H2OH 11m HO-CHz. C LCHIOH OHa-C-CHnOH The fourth category consists of polyamines having hydroxylated groups which may be characterized by the following:

Nonrmonauu noozn,

C 111 O H N C 2H4 O C a lN H O C zHi C Ha H N propyleneNpropyleneN HO C2114 CHL CH; CH:

Suitable cyclic amidines which may or may not have a hydroxyl group but are free from primary amino groups may be illustrated by the following:

oirnorr A compound having no basic secondary amino radical but a basic primary amino radical can be reacted with a mole of an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, etc., to yield a perfectly satisfactory reactant for the herein described condensation procedure. This can be illustrated in the following manner by a compound such as N-CH, C nHss-C N -CH1 CQHLNH:

2-heptadecy1-1-nminoethy1imidazoline which can be reacted with a single mole of ethylene oxide, for example, to produce the hydroxy ethyl derivative of Z-heptadecyl-l-aminoethylimidazoline, which can be illustrated by the following formula:

OrvHar-C Other reactants may be employed in connection with an initial reactant of the kind described above to wit, 2-heptadecyl-l-aminoethylimidazoline; for instance, reaction with an alkylene imine such as ethylene imine, propylene imine, etc. If reacted with ethylene imine the nets.

result is to convert a primary amino radical into a secondary amino radical and also introduces a new primary amine group. If ethylene imine is employed, the net result is simply to convert Z-heptadecyl-l-aminoethylimidazoline into 2-heptadecyl-l-diethylenediaminoimidazoline. However, if propylene imine is used the net result is a compound which can be considered as being derived hypothetically from a mixed polyalkylene amine, i. e., one having both ethylene groups and a propylene group between nitrogen atoms.

PART 3 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is diflicult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

The herein described amine-modified resins are obtained from alpha-hydroxyadipaldehyde and not formaldehyde. Generally speaking, the objective in thet preparation of these amine-modified resins is to obtain a heatconvertible compound even by using formaldehyde. It is not necessary to point out the complications involved when alpha-hydroxyadipaldehyde is used. See, for example, U. S. Patent No. 2,031,557 to Bruson. Since the condensation products obtained are not heat-convertible and since temperature up to C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures in a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact,

usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus,

we have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C, A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively nonvolatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as noted, and it is not necessary to have a single phase system for reaction.

Alpha-hydroxyadipaldehyde is available as a 50-55% aqueous solution. In this way it is comparable to formaldehyde which is available as a 37% aqueous solution, and is sometimes used in more dilute form. I have found no difficulty in promoting the condensation reaction although at times it is desirable to add some solvent having a common solvent effect. Thus an oxygenated solvent may or may not be employed. Such solvent may be employedin combination with a hydrocarbon solvent such as xylene. However, if the reaction mass is going to :be subjected to some further reaction where the "solvent may he objectionable as in the case of ethyl or hexyl alcohol, and if there .is to be subsequent oxyalkylation, then, obviously, the alcohols should not be used or else 10 In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over 15 (1 C. and employing vacuum if required. This applies, of course, only to those circumit should be removed. The fact that an oxygenated 5 stances where it is desirable or necessary to remove the SOIVeHt need not p y Of Course, is an advantage solvent. Petroleum solvents, aromatic solvents, etc., can for reasons stated. be used. The selection of solvent, such as benzene, J Another factor, as far as the selection of solvent goes, xylene, or the like, depends primarily on cost, i. e., the 'IS'WhCtheIOI' not the c generlc mlXtllre O tain d at th use of the most economical solvent and also on three e of the reaction q d as s r in th s other factors, two of which have been mentioned previ- 'f The h E Q lohtalhed are P] t0 he ously; (a) is the solvent to remain in the reaction mass solids or thlck F PP qh 1h h there some without removal? (b) is the reaction mass to be subjected ihe lhlhfil Teslh Itself, p y If some to further reaction in which the solvent, for instance, an of {he 111111131 solvent P h p alcohol, either low boiling or high boiling, might inter- Temoval- Y one Starts Wlth Whlch 1S ahhost 15 fere as in the case of oxyalkylation? and the third factor waterrwhite n color, the wnflensatwn p q Obtained is this (0) is an effort to be made to purify the reaction 5:11'8 invariably dark and particularly reddish 01' dark red mass by the usual prgcedure as for example a water- 11h wash to remove any unreacted low molal soluble amine, Y and l' r the mehlhg P0111t of the Condensate 15 if employed and present after reaction? Such procedures P} be higher than of comparable condensates P are well known and, needless to say, certain solvents are mined by the use formaldhhyde fhTfhraL AS has more suitable than others. Everything else being equal, been suggested previously, this apparently is du t the we have found xylene the most satisfactory solvent. 'dlfhhctmhal PF P Y of hlpha'hydmxyadlpaldehYhe- I have found no advantage in using a low temperature, Indeed, depending on the resin selected and the amine approximately room temperature at the Start of the selected the cohdehsate Prodhht or reachhh mass action although this is sometimes done purely as a matter Y h aPhtO harder than the onglhal of convenience. Indeed, using alpha-hydroxyadipalde- .resin itself. This is particularly true WEED all the amino hyde I have usually done nothing more than prepare the hydrhgeh atoms Preshht the amlhe ave'ehtered reaction mixture, add a suitable amount of xylene, and h hb d h reflux for approximately 3 to 6 /2 hours at temperatures Pmducgs h l g mg 6 55 varying, as the case may be, from 135 to 160 C. Where gi e i i g or Y g i s the amine has a comparatively low basicity I have someh f' f or 056 0 emg Wa i times added a small amount or approximately 1% of solubihty is enhanced, of course, by making a solution sodium methylate the g g i 2: 2 igz iga i gg' However, using a xylene-benzene mixture, for instance, ii g a z 3 also ma covert the approximately 170 parts of benzene and 35 parts of roxyace 6 9 y xylene, and a phase-separating trap to eliminate water, I shed product mm Salts by slmply adding a St01chl0 have found that I could em 10 tern ratures between metric amount of any selected 'acid and removing any 9 o d 100 C d l P g P f d water present by refluxing with benzene or the like. In 0 an f e Inmate t 6 water 0 con ehsahoh 'fact, the selection of the solvent employed may depend 40 by reflhxlhg at thls h h Bowevhr, I have found in part Whether or not h product at h l ti f no particular advantage in using this low temperature over the reaction is to be converted into a salt form. and above the high temperature previously noted.

TABLE II Alpha- Solvent hydroxy (xylene Max. Resin Amt, adipalunless Time temp. Ex. No. amt, 1 Secondary amine grams dehyde otherwise period, during grams noted), hrs. reaction,

aq. s01 grams 0.

grams 175 61 30. 0 190 7. 0 145 150 65 65. 0 164 6. 0 153 150 37 65. 0 154 6. 0 144 150 91 65. 0 150 6. 0 167 300 37 130. 0 306 5. 143 300 Di-2-ethylhexylamine 241 130.0 237 5.5 164 225 Bis- 1, 3-dimethy1bi1tyl) 51111115.... 139 97.5 238 225 Di-iso lalropanolamine 97. 5 232 3. 5 166 225 a-Met ylbenzyl-ethanolamine 124 97.5 237 3.5 160 225 Di-ethanolamine 79 97. 5 222 3. 5 101 225 Aminoethyl ethanolamine 78 97. 5 234 2. 5 146 225 Diethanolamine 79 97. 5 "55-170 4. 0 107 225 o 79 97.5 "55-170 4.0 100 225 do 131.5 123 "55-170 4.0 101 225 Diisopropanolamine 174 173. 0 238 2. 0 125 236 Di-is0propy1arnine 61 so. 0 235 7. 5 197 Di-n-butylamme-.. 65 65. 0 194 6. 5 166 197 Di-ethylamine 37 65.0 203 5.5 148 197 91 65. 0 173 6. 5 156 393 37 130. 0 377 6. 75 160 393 241 130. 0 398 6. 0 166 197 54 65. 0 100 5. 0 167 295 169 97. 5 302 5. 5 160 295 100 97. 5 204 4. 0 150 225 79 97. 5 298 a. 0 143 188 61 so. 0 220 7. 5 168 13s 65 65. 0 131 6. 0 150 188 37 65. 0 177 6. 5 162 374 Di-cyclohexyla me 91 65:0 193 7.0 163 374 Morphollne 87 130. 0 373 7. 5 13s Di-(2-ethylhexyl)amine 241 130 377 5. 5 166 280 N-methylsiniline 54 65 201 6. O 167 280 Di(heta-phenylethy1)amine- 169 97. 5 295 6. 5 156 280 Di-isopropanolerniue. 100 .97. 5 272 4. 5 158 280 Di-ethanolamlne 79 97. 5 273 3. 0 156 Example 1b The resin employed was the one previously designated as 28a and had a molecular Weight of approximately 600'. 175 grams of this resin were dissolved in slightly more than an equal weight of xylene and 61 grams of diisopropanolamine added. 80 grams of alpha-hydroadipaldehyde (50% aqueous solution) were added and the mixture stirred for about 40 minutes andthen the temperature allowed to rise to 142 C., where it was allowed to reflux for 7 hours at a maximum temperature of 145 C. During this refluxing period a phase-separating trap was used to remove the water of formation, and also the water of solution. At the end of this time the reaction was complete and the product was obtained in the form of a xylene solution. A small sample was evaporated to eliminate the xylene. The resultant product was an almost hard somewhat tacky material, being blackish red in color.

Similar products were prepared as indicated in Table II.

NorE:In the above examples no catalyst was added. In some duplications of the above small amounts of catalyst were added up to 1% to 2% of either powdered caustic soda or powdered sodium methylate. No advantage was noted in the use of a catalyst provided the amine was sutliciently basic.

In Examples 12b, 13b and 14b indicated by the double asterisk the solvent was a mixture of 170 parts of benzene and 55 parts of xylene.

The molal ratio of resin to amine to aldehyde was 1 to 2 to 1, except in Examples 14b and 15b where the ratio was 1 to 3.5 to 1.75 in both instances.

In Examples 1b through 15b the resin employed was the one identified as Example 28a. In Examples 16b through 2511 the resin employed was the one identified as Example 32a, and in Examples 26b through 35b the resin employed was identified as Example 39a.

Returning now to a consideration of the structure of the condensate it becomes obvious that one could obtain ring compounds. Using the abbreviated formula previously applied, the simplest ring could be shown thus:

Obviously, one could have rings with a larger number of members in the ring to say nothing of complications involving alkanol radicals, for instance, the elimination of a hydrogen atom from the alkanol hydroxyl group.

Furthermore, the situation becomes even morecompli 4 cated if the ratios are changed to correspond to ratiosdescribed in my co-pending application, Serial No tible to oxyalkylation. Indeed, another variety of somewhat more complicated materials are obtained by using as the amine reactant di('hydroxyethyl)N,N-ethylene diamine having the following-structure:

HO 01H; H

NGa AN H CQHtOH If corresponding conQ An initial product can be made treating the amine as if it were nothing more than a hydroxylated monoamine. Subsequently alpha-hydroxyadipaldehyde may be added up to, for example, the amount originally employed with the production of linear polymers and in some instances cross-linking. It is understood that regardless of what amine is used the final product obviously is, and must be, organic solvent-soluble. The primary objective is toobtain a condensate which is organic solvent-soluble and not an infusible resin. Such condensate is particularly valuable for oxyalkylation. The products so obtained find utility in various art-s. 1

See my co-pending application, Serial No. 383,928 filed October 2, 1953, now Patent No. 2,792,366, dated May 14, 1957. This particular application is essentially the same as the instant application except that glyoxal is used instead of alpha-hydroxyadipaldehyde. It is well known that alpha-hydroxyadipaldehyde enters into a number of reactions which would not be expected to appear in the use of glyoxal. For instance, alpha-hydroxyadipaldehyde tends to polymerize and, indeed, aqueous solutions of alpha hydroxyadipaldehyde coated on wood, metal,'textiles, etc., lose water rapidly to yield clear, substantially insoluble, irreversible polymers.

PART 4 At the present time there are available a number of alkylene oxides, particularly ethylene oxide or propylene oxide and butylene oxide, either as a single isomer or as a mixture of isomers. Glycide is available, or readily prepared. The same applies to methyl-glycide.

Oxyalkylation with any of the aforementioned alkylene oxides is comparatively simple in light of present day knowledge. In fact, it is stated briefly in U. S. Patent No. 2,636,038, dated April 21, 1953, to Brandner, in the following language: The compounds are pre pared by the addition reaction between alkylene oxides and substituted oxazolines of the group named hereinbefore. The addition reaction is advantageously carried out at elevated temperature and pressure and in the presence of an alkaline catalyst. 7

As to a more complete description of oxyalkylation procedure reference is made to U. S. Patent 2,629,706, dated February 24, 1953, to De Groote and Keiser. See particularly the subject matter which appears in column 7 of said patent.

Propylene oxide and butylene oxide react somewhat more slowly than ethylene oxide and may require a somewhat higher temperature, somewhat greater agitation, or an increased amount of alkaline catalyst, such as finely powdered sodium hydroxide or sodium methylate. If the product to be subjected to oxyalkylation is xylenesoluble or soluble in any one of a number of inert solvents, there is no particular difficulty involved. The same is true if the product is a liquid at oxyalkylation temperatures. If it is not soluble or a liquid then in some cases initial oxyalkylation can be accomplished by means of an alkylene carbonate, such as ethylene carbonate or propylene carbonate which has a solubility effect as well as acting as an oxyalkylation agent. As soon as a suitable product is obtained by the use of a carbonate further reaction can be completed with the oxide. An alternate procedure sometimes employed with insoluble materials is to reduce the products to an extremely finely ground powder and oxyalkylate during suspension using particularly vigorous agitation.

All these procedures have been described repeatedly in the literature and, as a matter of fact, suitable operational directions are available from any one of several makers of alkylene oxides.

, Example 10 Due to their ready availability, the bulk of the oxyalkylation derivatives were prepared from ethylene oxide, propylene oxide, butylene oxide, or a mixture of the same.

13 Generally speaking, the autoclaves or oxyalkylators employed ranged from approximately 2 gallons in size to approximately 20 gallons in size. The general procedure was to start with a fairly small sample; for instance, approximately 2000 grams, of the product to be oxyalkylated and 1000 grams of a solvent such as xylene, or a highboiling aromatic solvent, or the 'diethylether of ethyleneglycol, or a mixture of these solvents. Powdered caustic soda, or sodium methylate, were added as a catalyst-in an amount generally not over 2%, and more catalyst was added if the amount dropped to /z% or less.. Initial oxyalkylation generally started by adding 50% by weight, 100% by weight, 200% by weight, 300% by weight, 500% by weight, etc., until at least ten times as much oxide had been added, at least in some examples. Excellent compounds or suitable raw materials have been obtained by adding as much as 50 parts by weight of oxide to one part of the initial reactant. In some instances the same examples were repeated and then reacted with one or more oxides; for instance, in the table which follows there are examples where an oxyethylated product was oxypropylated subsequently, or vice-versa. Comparatively small samples, for instance, one to five grams, were taken at various stages and tested for emulsifiability factor and also for demulsifying efiect on crude oil emulsions. The tabular data do not reflect the slight discrepancy due to sample withdrawal.

More specifically then, 18 pounds (5,200 grams) of the condensate previously identified as Example 1b, were mixed with approximtaely two-thirds, actually 12 pounds of solvent (being xylene in this series). The mixture was placed in a small autoclave together with 162 grams of finely powdered caustic soda, and stirred, and the temperature raised to approximately ll115 C. 9 pounds of ethylene oxide were added in approximately 25 to 30 minutes. The pressure during the oxyalkylation was about 25 to 30 pounds per square inch. The resultant product was a viscous liquid having a reddish black cast. Except for the withdrawal of a few grams for examination, the product was then subjected to further oxyalkylation with another 9 pounds of ethylene oxide and without the addition of any more catalyst or any more solvent.

Note what is said in regard to these examples and subsequent examples in the text immediately following, and in the tables.

A number of additional examples appear in tabular form in the five tables immediately following, to wit, Tables III, IV, V, VI and VII. These are self-explanatory, particularly in regard to the first three tables. The last two require a little more careful examination. This is due to an elfort to condense the data and not burden the text with an unduly large volume of detail.

Due to the fact that various size quantities are used the ratios sometimes appear in grams or kilograms and sometimes in pounds. When pounds are used the designation is included.

In Tables III, IV and V successive stages of oxyalkylation are shown. Small samples of a few grams were withdrawn and tested for solubility and also for demulsification effectiveness. The withdrawal of such small samples was ignored. In some instances the example was repeated and used subsequently for reaction with one or more other oxides. In some instances the product was so obtained in the first stage of oxyalkylation represented a comparatively large quantity and was subdivided perhaps into one-half or even a smaller fraction, and then this smaller fraction only subjected to oxyalkylation with another oxide. As previously noted, no further explanation is required in regard to the first three tables.

In the fourth table, Table VI, it is to be noted that Example 1 is derived from Example 7c. Referring to Example 7c it will be noted this was derived originally from oxyalkylation-susceptible compound Example 1b. In Example 70, oxyalkylation-susceptible compound Example 1b had already been treated with ethylene oxide. Thus, in Table'Vl, although the oxyalkylation-susceptible compound is properly designated as Example 70 for the reason it is now the reactant subjected to oxybutylation, the oxyalkylatiOrr-susceptible compound as far as reference to weight goes (in this instance 18 pounds) goes back to the original compound Example 1b. This isobvious, and is even more obvious for the reason that it is subsequently emphasized in connection with the weight ratio, as explained subsequently.

It will be noted also that in the fourth column in Table VI the oxide used is marked as indicated and in each instance the oxide employed in this second stage is shown, in one instance in Table VI being butylene oxide, in another instance ethylene oxide, and in another instance propylene oxide.

Bearing in mind what is said in regard to Example 1 being derived from Example 70, which in turn was derived from Example 1b plus ethylene oxide, it should :be noted that this table does not, as far as the first four columns go, reflect the amount of oxide which was added in the initial or earlier stage. As previously noted, this does not cause confusion and, in fact, permits holding the data to a minimum in light of what is said next.

Referring now to columns seven, eight, nine and ten which are concerned with composition at the end, it will be noted that these data do take into consideration the amount of oxide added initially as well as the oxide during the second stage. Thus, although this shows the butylene oxide added it also shows the original ethylene oxide as representing the four-to-one weight ratio based on the oxyethylation of the first stage. This can be stated perhaps more simply in the following way: 'On initial examination the table shows that Example 1 was derived from Example 70. As to the composition .of Example 7c one need only note that in the seventh column it shows that 1000 grams (one kilo) of butylene oxide were added and the weight ratio to the oxyalkylationsusceptible compound Example 1b was .33 to 1, but it also shows that the weight ratio of the ethylene oxide at the same stage was four-to-one. Thus, without even checking back to a prior table it is obvious the initial material, Example 7c, subjected to a second oxyalkylation step, consisted of a product in which one pound of the oxyalkylation-susceptible compound was combined with 4 pounds by Weight of ethylene oxide, prior to oxybutylation.

Since 1 kilogram of butylene oxide was used which is equivalent to 2.2 pounds, which was equivalent to onethird part by weight of the oxyalkylation-susceptible compound Example lb, it means in essence that 3 pounds or 3 kilos of the oxyalkylation-susceptible compound had previously been combined with four times its weight of ethylene oxide, i. e., 12 kilos or 12 pounds of ethylene oxide and is now being combined with one-third its weight, .33 kilo or .33 pound, of butylene oxide. Actually what has been shown in pounds can be ignored for all these happen to be in kilograms. Referring back to Example 70 it will be noted that the ratio of ethylene oxide to initial oxyalkylation-susceptible compound was fourto-one.

All the data in Tables VI and VII are presented in the same way. We find this is the most simple and concise tabular presentation that yet has been developedafter a considerable series of experimentations, and reports in table form. This is true even where three oxides were employed as for instance in Example 1g in Table VII. Example 1g was obtained from Example 5] in Table VI. Example 5f, as indicated, was obtained by an oxybutylation of Example If, and Example If, as previously noted, was obtained from Example 70. The preparation of Example 70 from Example 1b has been discussed in considerable detail in the previous text. Again it :is to be noted that in the tables the ratios of the oxide to the initial product prior to oxyalkylation is shown so there 15 is no question as to the composition of each example although considerable data have been presented in what is a comparatively condensed and readily understandable form.

Note what is said in regard to the color of the products in the tables. For most industrial purposes there is no objection to the color. The products can be decolorized by conventional procedure, using bleaching earths, filtering clays, charcoal, or the like. A trace or small amount of catalyst, if present, can be removed for most purposes by the mere addition of a comparable amount of hydrochloric acid or by any other suitable means.

Having thus described my invention, what I claim as new and desire to obtain by Letters Patent is:

1. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule;

TABLE III Composition beforeAmount of 050, catalyst anld solvent constant before and after oxyalkyl- Composition at end Operating conditions a on Ex. Weight ratio End product- N 0. Color and physical OSC 1 X1 d e Cata- Xylene O we Max. Max. Time state Ex. 050 1 used Eto lyst, solvent, usedx Eto EtO to PrO to BuO to pres., temp., of re- No. grams ams NaOH, grams rams 2 oxyalkyloxyalkyloxyalkylp. s. 1. C. action, gr grams g ation ation ation hrs.

suscept. suscept. suscept. empd. empd. cmpd.

1a-.-. 1b- 18.# 0# 162 12. 9. 0# 0.5 110-115 14 Reddish black viscous liquid. 2c 1c.- 18. 0 9. 0 162 12.0 18. 0 1. 0 110-115 }4 go-.-" 18.3 162 12.0 25.2 Lg c.-. 25. 162 12.0 32. 4 1. 4 50-.-. 4c 18. 0 32. 4 162 12. o 36.0 2. 0 110115 y g g gg 5c 18.0 36.0 162 12.0 54.0 3. 0 110-115 )2 color be a 7c... 6c- 9. 0 27.0 162 6. 0 36. 0 4. o 110-115 g l. 8c 70..." 9. 0 36.0 162 6. 0 72. 0 8.0 110-115 2 2 er but gi 9a--.- 80... 17.5 0 225 16. 5 17.5 1.0 110-115 1 increased until y 106... 91:... 17.5 17.5 225 16.5 26.2 1.5 110-115 the last Sam 19 11cc 17.5 26. 2 225 16. 5 30. 6 1.75 110-115 was a solid 1 110-..- 17. 5 30. 6 225 16. 5 35. 0 2. 0 110-115 semisolid 130... 126.... 17. 5 35.0 225 16.5 45. 5 2.6 110-115 1 14c. 136-- 8. 75 22. 75 225 8. 25 35. 0 4. 0 110-115 1% 15c--. 14c 8.75 35. 0 225 8. 25 70.0 8. 0 110-115 3 1 Oxyalkylstlon-susceptible compound. In some instances weights change from gram basis to pound basis. Such change in unit is obvious.

TABLE IV Composition before-Amount of 0S0, catalyst aitnid solvent constant before and after oxyalkyl- Composition at end Operating conditions a on Ex. Weight ratio End product- No. Color and physical 050 l Oxide Cata- Xylene Oxide Max. Max. Time state 113x. 080 1 used Pro I\lysotl,I solvent used Pro Eflgkto1 Prqkto1 Bu(1)kt; i pres}, tang) ogreo. grams a grams oxya y oxya y oxya p. s. ac 1011,

grams grams grams 2 ation etion hrs.

suscept. suscept. suscept. cmpd. cmpd. cmpd.

21 0# 0# 900 0# 2.0 120-125 4% Reddish black viscous liquid. 21. 0 42. O 900 20. 0 4. 0 120-125 5 Do. 10. 5 42. 0 450 10. 0 8. 0 120-125 5 Do. 5. 25 42. 0 225 5. 0 12.0 120-125 8 Do. 5. 25 63.0 225 5.0 15.0 120-125 4 Do. 3. 15 47. 25 135 3. 0 18. 1 120-125 3 D0. 3.15 57 0 135 3.0 25.0 120-125 5% Do. 3. 15 78 135 3. 0 27. 9 120-125 4 D0. 16. 0 720 14. 0 4. 37 120-125 6% D0. 8.0 55. 0 360 7.0 10. 62 120-125 5 Do. 4. 0 42. 5 180 3. 5 18. 0 120-125 3% D0. 4. 0 72.0 180 3. 5 21. 4 120-125 2% Do. 2. 0 42. 75 1. 75 25. 0 -125 1% D0. 2.0 50.0 90 1. 75 28.0 120-125 2 D0. 2.0 56. 0 90 1. 75 30. 0 120-125 2 Do.

1 Oxyalkylation-susceptible compound.

1 In some instances weights change from gram basis to pound basis. Such change in unit is obvious.

PART 5 Asto the use of conventional demulsifying agents reference is made to U. S. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part Three. Everything that appears therein applies with equal force and eifect-to the instant process, noting only that Where -reference is made to Example 13b in said text beginning :in column '15 and ending in column 18, reference should .-,-be 't o;Ex ample 6c, herein described.

TABLE V Composition before-Amount of 080. catalyst apid solvent constant before and alter oxyalkyl- Composition at end Operating conditions a on Ex. Weight ratio End product- No. Color and physical S0 l 0 Oata- Xylene 0 id Max. Max. Time state 113x. OSC 1 use 3 Nlyg],I solvent usedx 3 EtClikto1 Prqkto1 BuCfktti pres. t ng) oigirc- 0. grams a ams oxya y oxya y oxya y p. s. 1. ac on,

grams grams gr grams 2 ation ation ation hrs.

suscept. suscept. suscept. cmpd. cmpd. cmpd.

35. 0# 03 675 30. 0# 485 -30 130-135 2% Grecnish black vis cous liquid. 35. 0 17. 0 675 30. 0 1. 0 25-30 130-135 2% Do. 17. 5 l7. 5 337. 5 15. 0 1. 5 25-30 130-135 2 D0. 17. 5 26. 25 337. 5 15. 0 2. 0 25-30 130-135 2 D0. 17. 5 35.0 337. 5 15.0 2.46 25-30 130-135 3 D0. 18. 0 0 810 18.0 1. 0 25-30 130-135 2% Dark amber to black viscous liquid. 18. 0 18.0 810 18. 0 2. 5 25-30 130-135 4% Do. 18. 0 45. 0 810 18. 0 3. 0 25-30 130-135 2 Do. 9. 0 27. 0 405 9. 0 4. 2 25-30 130-135 2% D0. 9. 0 37. 8 405 9. 0 5. 5 25-30 130-135 3 Do. 21. 0 0 495 23. 0 9 25-30 130-135 3 Do. 21.0 18.9 495 23.0 1. 2 25-30 130-135 1% D0. 21. 0 25. 2 495 23. 0 2. 5 25-30 130-135 5 Do. 11. 5 26. 25 247. 5 11. 5 3. 7 25-30 130-135 4 Do. 11.5 42. 5 246. 5 11. 5 5. 0 25-30 130-135 4 D0.

1 Oxyalkylation-susceptible compound. 2 In some instances weights change from gram basis to pound basis. Such change in unit is obvious.

TABLE VI Composition before-Amount of 080, catalyst apid solvent constant before and after oxyalkyl- Composition at end Operating conditions a on Ex. Weight ratio End product- No. Color and physical 080 1 Oxide Cata- Xylene Oxide Max. Max. Time state Ex. 080 1 used, as lyst, solvent used, as EtO to PrO to BuO to pres., temp., of re- No. grams indicated, NaOH, grams indicated, oxyalkyloxyalkyloxyalkylp. s. i. 0. action,

grams grams grams 2 ation ation ation hrs,

suscept. suscept. suscept. cmpdfi cmpdfl cmpd.

1f 7c-. 3.0 Kg 0 Kg.BuO 300 2.0 Kg 1.0 Kg.BuO 4.0 .33 25-30 125-130 1% Reddish black Eeavy viscous 0 3.0 1.0 300 2.0 2.0 4.0 .67 25-30 125-130 1% Viscous liquid. 3. 0 2. 0 300 2. 0 3. 0 4. 0 1. 0 25-30 125-130 2 D0. 3.0 3. 0 300 2. 0 4. 5 4.0 1. 5 25-30 125-130 2% Do. 3.0 4.5 300 2.0 12.0 4.0 4 0 25-30 125-130 8% D0. 1. 0 0 E130 100 1.14 1.0 EtO 1.0 25-30 125-130 D0. 1. 0 1. 0 100 1. 14 1. 3 1. 3 25-30 125-130 34 Do. 1. 0 1. 3 100 1. 14 2. 4 2. 4 25-30 125-130 1% D0. 1. 0 2. 4 100 1. 14 4. 0 4. 0 25-30 125-130 1% D0. 1. 0 4.0 100 1. l4 9. 6 9. 6 25-30 125-130 5 D0. 1. 28 0 H0 130 1. 28 5. 0 25-30 125-130 2% Dark amber viscous liquid. 1. 28 6.4 130 1. 28 5.0 25-30 125-130 2% Do. 64 6. 4 65 64 5.0 25-30 125-130 2 D0. 64 10. 0 65 64 5. 0 25-30 125-130 1 D0. 64 12. 8 65 64 5. 0 25-30 125-130 1% DO.

1 Oxyalkylation-susceptible compound.

In some instances weights change from gram basis to pound basis. Such change in unit is obvious. Weight ratio based on original oxyalkylation-susceptible compounds prior to any oxyalkylation.

in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2, 4, 6 position; (b) a basic secondary amine free from any primary amino radical and having not more than 32 carbon atoms in any group attached to any amino nitrogen radical and reactive towards alpha-hydroxyadipaldehyde; and (c) alpha-hydroxyadipaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oXyalkylation-susceptible; followed by a second step of reacting said condensate with an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

60 be an alkanol radical attached to at least one amino nitrogen atom.

3. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyalkylatiou-susceptible, fusible, non-oxygenated organic solventsoluble, Water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of TABLE VII Composition before-Amount of 080, catalyst aiild solvent constant before and after oxyalkyl- Composition at end Operating conditions a on 113x. Weight ratio c lind plg'idlficli 1 o. or an p ysioa 080 l Oxide Gata- Oxide Max Max. Time state Ex. C 1 used, as lyst, Solvent used, as EtO to PrO to BuO to pres temp, of re- No. grams indicated, NaOH, grams indicated, oxyalkyloxyalkyloxyalkylp. s. 1 0. action,

grams grams grams 2 ation ation ation hrs.

suscept. suscept. suscept. enipd. crnpd. cmpdfi 1a-.- 51'.-- Kg 0 Kg.PrO 150 1.0 Kg 6.0 Kg.PrO 4.0 4.0 4.0 -30 125-130 3% Reddislh bliadck viseous iqu 2a--.- 10- 1. 5 6.0 150 1.0 12.0 4.0 8.0 4.0- 25-30 125-130 3% D0. 3a---- 2a--- 75 6. 0 75 .5 7. 5 4. 0 10.0 4. 0 25-30 125-130 3/4 Do. 4g 75 7. 5 75 .5 10. 4.0 14.0 4.0 25-30 125-130 1% D0. 50-.-- 4g 75 10.5 75 .5 12. 0 4. 0 16.0 4. 0 25-30 125-130 1% Do. 69"..- 10].-.- 0. 5 0 BuG 50 57 2.0 BuO 0. 6 18.0 4. 0 25-30 125-130 3 D0. 70---. 6g-- 0. 5 2. 0 50 57 2. 8 9. 6 18.0 5. 6 25-30 125 130 1 Do. 89---. 7g... 0.5 2. 8 50 57 3. 5 9. 6 18.0 7.0 25-30 125-130 1 Do. 90--.. 80---... 0. 5 3. 6 50 57 4. 8 9. 6 18.0 9. 6 25-30 125-130 2 DO. 109... I)... 0. 5 4. 8. 50 .57 5. 5 9. 6 18.0 11.0 25-30 125-130 2 D0. 110. 13].--. 64 0 EtO 65 64 .64 INC 1. 0 15. 6 5. 0 25-30 125-130 Dark alliiilbdllviS- oOus qui G4 64 65 64 1. 28 2. 0 i5. 6 5. 0 25-30 125-130 Do.

0xyalkylation-susceptible compound. In some instances weights change from gram basis to pound basis.

Such change in unit is obvious.

I Weight ratio based on original oxyalkyiation-susceptible compounds prior to any oxyalkylation.

in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2, 4, 6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards alpha-hydrox-yadipaldehyde; and (0) alphahydroxyadipaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolyt-ic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by a second step of reacting said condensate with an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

4. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyalkylanon-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radica lhaving at least 4 and not more than 24 carbon atoms and substituted in the 2, 4, 6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards alphahydroxyadipaldehyde; and (c) alphahydroxyadipaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the added proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule; and with the further proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susccptible; followed by a second step of reaction said condensation with an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

5. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule;

said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula beingconducted at a temperature sufficiently high to eliminatewater and below the pyrolyticpoint of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by-virtue of an alpha-hydroxyadipaldehyde-derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the further-proviso that the ratio of reactants be approximately 1, 2 and 1 respectively; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by a second step of reacting said condensate with an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycicle.

6. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier includingsyntheti-c hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards alpha-hydroxyadipaldehyde; and (0) alphahydroxyadipaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of an alpha-hydroxyadipaldehyde-derived substituted methylene bridge connecting the amino nitrogen atom with a resin molcule; with the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively, with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by a second step of reacting said condensate with an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

7. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said in which R is an aliphatic hydrocarbon radical having-at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards alpha-hydroxyadipaldehyde; and (0) alphahydroxyadipaldehye; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactantsand resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of an alpha-hydroxyadipaldehyde-derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by a second step of reacting said condensate with an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

8. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards alpha-hydroxyadipaldehyde; and (0) alphahydroxyadipaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of an alpha-hydroxyadipaldehyde-derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process of the I 2 .3 bobcat-stable and oxyalkylationsusceptible; followed by asecond ;step of reacting said condensate with an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

9. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, 10v -stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards alpha-hydroxyadipaldehyde; and (0) alphahydroxyadipaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants-of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of an alpha-hydroxyadipaldehyde-derived substi tuted methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be. heat-stable and oxyallcylation-susceptible; followed by a second step of reacting said condensate with an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene "oxide, glycide and methylglycide.

10. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products, said synthetic hydrophile products being the products resulting from a two-step manufacturing process consisting of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said .resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than 2; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom and reactive towards alpha-hydroxyadi'paldehyde; and (0) alpha hydroxyadipaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of an alpha-hydroxyadipaldehyde-derived substituted methylene bridge connecting the amino nitrogen atom with a resin molecule; With the added proviso that the ratio of reactants be approximately 1, 2 and 1, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by a second step of reacting said condensate with an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

References Cited in the file of this patent UNITED STATES PATENTS 2,454,545 Bock et a1. Nov. 23, 1948 2,457,634 Bond et al Dec. 28, 1948 2,507,910 Keiser et al May 16, 1950 2,558,688 Landa June 26, 1951 2,589,200 Monson Mar. 11, 1952 2,695,887 De Groote Nov. 30, 1954 

1. THE PROCESS OF BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING SYNTHETIC HYDROPHILE PRODUCTS, SAID SYNTHETIC HYDROPHILE PRODUCTS BEING THE PRODUCTS RESULTING FROM A TWO-STEP MANUFACTURING PROCESS CONSISTING OF FIRST CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN 2; SAID PHENOL BEING OF THE FORMULA 